Difference between revisions of "Hypofluorous acid"

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(Created page with ''''Hypofluorous acid''' or '''oxygen fluoride hydride''', HOF, is an unstable compound arising from the reaction of gaseous fluorine with water. It was first isolated in weig…')
 
 
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'''Hypofluorous acid''' or '''oxygen fluoride hydride''', HOF, is an unstable compound arising from the reaction of gaseous [[fluorine]] with water. It was first isolated in weighable quantities in 1971.
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{{FixBunching|beg}}
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{{chembox
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| IUPACName = fluoranol
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| OtherNames = oxygen fluoride hydride
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| Section1 = {{Chembox Identifiers
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|  CASNo = 14034-79-8
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|  ChemSpiderID = 109936
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|  InChI=1/FHO/c1-2/h2H
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|  StdInChI=1S/FHO/c1-2/h2H
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|  InChIKey = AQYSYJUIMQTRMV-UHFFFAOYAN
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|  StdInChIKey = AQYSYJUIMQTRMV-UHFFFAOYSA-N
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|  EC-number =
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  }}
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| Section2 = {{Chembox Properties
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|  Reference = <ref name="G&E">{{Greenwood&Earnshaw1st|page=1003}}.</ref>
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|  Formula = HOF
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|  MolarMass = 36.006 g mol<sup>−1</sup>
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|  Appearance = ''see text''
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|  Density =
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|  MeltingPt = −117 °C
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|  BoilingPt = < 0 °C
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|  Solubility = reacts
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  }}
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| Section3 = {{Chembox Structure
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|  Reference = <ref>{{citation | journal = J. Chem. Phys. | volume = 56 | issue = 1 | pages = 1–3 | year = 1972 | doi = 10.1063/1.1676830 | title = Millimeter‐Wave Spectrum and Structure of Hypofluorous Acid: HOF and DOF | first1 = Hyunyong | last1 = Kim | first2 = Edwin F. | last2 = Pearson | first3 = Evan H. | last3 = Appelman}}.</ref>
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|  MolShape = bent: H–O = 96.4(10) pm, O–F = 144.2(1) pm, H–O–F = 97.2(6)°
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|  SpaceGroup =
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|  Coordination =
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|  LattConst_a =
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|  LattConst_c =
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  }}
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| Section4 = {{Chembox Thermochemistry
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|  Reference = <ref>{{NIST chemistry | name = Hypofluorous acid | id = InChI=1S/FHO/c1-2/h2H | accessdate = 2010-09-17}}.</ref>
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|  DeltaHf = −98.32 kJ mol<sup>−1</sup>
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|  Entropy = 226.77 J K<sup>−1</sup> mol<sup>−1</sup>
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  }}
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| Section8 = {{Chembox Related
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|  OtherCpds = [[Hypochlorous acid]]<br/>[[Hypobromous acid]]<br/>[[Hypoiodous acid]]
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  }}
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}}
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{{chembox
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| Name = Rozen's reagent
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| IUPACName = acetonitrile—fluoranol (1/1)
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| Section1 = {{Chembox Identifiers
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|  CASNo =
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|  ChemSpiderID = 9226732
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|  InChI=1/C2H3N.FHO/c1-2-3;1-2/h1H3;2H
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|  StdInChI=1S/C2H3N.FHO/c1-2-3;1-2/h1H3;2H
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|  InChIKey = MHXSJBXDLWNIAN-UHFFFAOYAK
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|  StdInChIKey = MHXSJBXDLWNIAN-UHFFFAOYSA-N
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|  EC-number =
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  }}
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}}
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{{FixBunching|end}}
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'''Hypofluorous acid''', HOF, is an unstable compound arising from the reaction of gaseous [[fluorine]] with water. It was first isolated in weighable quantities in 1971.<ref name="1stPrep">{{citation | last1 = Studier | first1 = Martin H. | last2 = Appleman | first2 =  Evan H. | title = Hypofluorous Acid | journal = J. Am. Chem. Soc. | year = 1971 | volume = 93 | issue = 9 | pages = 2349–51 | doi = 10.1021/ja00738a059}}.</ref> Despite the name, formed by analogy with other halogen compounds of similar formula,<ref group="Note">For example, [[hypochlorous acid]], HOCl.</ref> HOF is not significantly acidic, and hypofluorite salts are unknown.
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A solution of hypofluorous acid in [[acetonitrile]] is significanly more stable that the pure compound, due to the formation of a [[Hydrogen bond|hydrogen-bonded]] [[adduct]], MeCN·HOF.<ref>{{citation | title = Epoxidation of Olefins with Elemental Fluorine in Water/Acetonitrile Mixtures | first1 = Shlomo | last1 = Rozen | first2 = Michael | last2 = Brand | journal = Angew. Chem. Int. Ed. Engl | volume = 25 | issue = 6 | pages = 554–55 | year = 1986 | doi = 10.1002/anie.198605541}}.</ref><ref>{{citation | first1 = Shlomo | last1 = Rozen | first2 = Yifat | last2 = Bareket | first3 = Moshe | last3 = Kol | title = HOF·CH<sub>3</sub>CN, made directly from F<sub>2</sub> and water, as an ecologically friendly oxidizing reagent | journal = Tetrahedron | volume = 49 | issue = 36 | year = 1993 | pages = 8169–78 | doi = 10.1016/S0040-4020(01)88036-4}}.</ref><ref>{{citation | first1 = Evan H. | last1 = Appelman | first2 = Oliver | last2 = Dunkelberg | first3 = Moshe | last3 = Kol | title = Hypofluorous acid and acetonitrile: the taming of a reagent | journal = J. Fluorine Chem. | volume = 56 | issue = 2 | year = 1992 | pages = 199–213 | doi = 10.1016/S0022-1139(00)81103-3}}.</ref> This species is sometimes called '''Rozen's reagent''', and is a strong [[oxidizing agent]] through oxygen transfer: it is particularly useful for [[epoxidation]] reactions.
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==Preparation==
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Reported preparations of hypofluorous acid in the 1930s<ref>{{citation | first1 = L. M. | last1 = Dennis | first2 = E. G. | last2 = Rochow | title = Oxyacids of Fluorine | journal = J. Am. Chem. Soc. | year = 1932 | volume = 54 | issue = 2 | pages = 832–33 | doi = 10.1021/ja01341a518}}.</ref><ref>{{citation | first1 = L. M. | last1 = Dennis | first2 = E. G. | last2 = Rochow | title = Oxyacids of Fluorine. II | journal = J. Am. Chem. Soc. | year = 1933 | volume = 55 | issue = 6 | pages = 2431–34 | doi = 10.1021/ja01333a033}}.</ref> are now considered erroneous.<ref name="1stPrep"/> The first clear observation of HOF was through the infrared spectrum of a [[matrix isolation]] sample, obtained by photolysis of a mixture of fluorine and water in a nitrogen matrix at 14–20&nbsp;K.<ref>{{citation | first1 = Paul N. | last1 = Noble | first2 = George C. | last2 = Pimentel | title = Hypofluorous acid: Infrared spectrum and vibrational potential function | journal = Spectrochim. Acta Part A | volume = 24 | issue = 7 | year = 1968 | pages = 797–806 | doi = 10.1016/0584-8539(68)80177-1}}.</ref>
  
 
==Notes and references==
 
==Notes and references==
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===References===
 
===References===
 
{{reflist}}
 
{{reflist}}
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===Further reading===
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*{{citation | title = The Crystal Structure of Hypofluorous Acid: Chain Formation by OH…O Hydrogen Bonds |
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first1 = Wolfgang | last1 = Poll | first2 = Gottfried | last2 = Pawelke | first3 = Dietrich | last3 = Mootz | first4 = Evan H. | last4 = Appelman | journal = Angew. Chem. Int. Ed. Engl. | volume = 27 | issue = 3 | pages = 392–93 | year = 1988 | doi = 10.1002/anie.198803921}}.
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*{{citation | first1 = Moshe | last1 = Kol | first2 = Shlomo | last2 = Rozen | title = Functionalization of aromatic molecules using HOF·CH<sub>3</sub>CN and CH<sub>3</sub>OF | journal = J. Org. Chem. | year = 1993 | volume = 58 | issue = 6 | pages = 1593–95 | doi = 10.1021/jo00058a052}}.
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*{{citation | first1 = Shlomo | last1 = Rozen | first2 = Michael | last2 = Brand | first3 = Moshe | last3 = Kol | title = Tertiary hydroxylation using fluorine: activation of the carbon–hydrogen bond | journal = J. Am. Chem. Soc. | year = 1989 | volume = 111 | issue = 21 | pages = 8325–26 | doi = 10.1021/ja00203a069}}.
  
 
==External links==
 
==External links==

Latest revision as of 13:34, 17 September 2010

Hypofluorous acid
IUPAC name fluoranol
Other names oxygen fluoride hydride
Identifiers
InChI InChI=1/FHO/c1-2/h2H
InChIKey AQYSYJUIMQTRMV-UHFFFAOYAN
Standard InChI InChI=1S/FHO/c1-2/h2H
Standard InChIKey AQYSYJUIMQTRMV-UHFFFAOYSA-N
CAS number [14034-79-8]
ChemSpider 109936
Properties[1]
Chemical formula HOF
Molar mass 36.006 g mol−1
Appearance see text
Melting point

−117 °C

Boiling point

< 0 °C

Solubility in water reacts
Structure[2]
Molecular geometry bent: H–O = 96.4(10) pm, O–F = 144.2(1) pm, H–O–F = 97.2(6)°
Thermochemistry[3]
Std enthalpy of formation ΔfHo298 −98.32 kJ mol−1
Standard molar entropy So298 226.77 J K−1 mol−1
Related compounds
Other compounds Hypochlorous acid
Hypobromous acid
Hypoiodous acid
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Rozen's reagent
IUPAC name acetonitrile—fluoranol (1/1)
Identifiers
InChI InChI=1/C2H3N.FHO/c1-2-3;1-2/h1H3;2H
InChIKey MHXSJBXDLWNIAN-UHFFFAOYAK
Standard InChI InChI=1S/C2H3N.FHO/c1-2-3;1-2/h1H3;2H
Standard InChIKey MHXSJBXDLWNIAN-UHFFFAOYSA-N
ChemSpider 9226732
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)

Hypofluorous acid, HOF, is an unstable compound arising from the reaction of gaseous fluorine with water. It was first isolated in weighable quantities in 1971.[4] Despite the name, formed by analogy with other halogen compounds of similar formula,[Note 1] HOF is not significantly acidic, and hypofluorite salts are unknown.

A solution of hypofluorous acid in acetonitrile is significanly more stable that the pure compound, due to the formation of a hydrogen-bonded adduct, MeCN·HOF.[5][6][7] This species is sometimes called Rozen's reagent, and is a strong oxidizing agent through oxygen transfer: it is particularly useful for epoxidation reactions.

Preparation

Reported preparations of hypofluorous acid in the 1930s[8][9] are now considered erroneous.[4] The first clear observation of HOF was through the infrared spectrum of a matrix isolation sample, obtained by photolysis of a mixture of fluorine and water in a nitrogen matrix at 14–20 K.[10]

Notes and references

Notes

  1. ↑ For example, hypochlorous acid, HOCl.

References

  1. ↑ Greenwood, Norman N.; Earnshaw, A. Chemistry of the Elements; Pergamon: Oxford, 1984; p 1003. ISBN 0-08-022057-6.
  2. ↑ Kim, Hyunyong; Pearson, Edwin F.; Appelman, Evan H. Millimeter‐Wave Spectrum and Structure of Hypofluorous Acid: HOF and DOF. J. Chem. Phys. 1972, 56 (1), 1–3. DOI: 10.1063/1.1676830.
  3. ↑ Hypofluorous acid. In NIST Chemistry WebBook; National Institute for Standards and Technology, <http://webbook.nist.gov/cgi/inchi/InChI%3DInChI=1S/FHO/c1-2/h2H>. (accessed 17 September 2010).
  4. ↑ 4.0 4.1 Studier, Martin H.; Appleman, Evan H. Hypofluorous Acid. J. Am. Chem. Soc. 1971, 93 (9), 2349–51. DOI: 10.1021/ja00738a059.
  5. ↑ Rozen, Shlomo; Brand, Michael Epoxidation of Olefins with Elemental Fluorine in Water/Acetonitrile Mixtures. Angew. Chem. Int. Ed. Engl 1986, 25 (6), 554–55. DOI: 10.1002/anie.198605541.
  6. ↑ Rozen, Shlomo; Bareket, Yifat; Kol, Moshe HOF·CH3CN, made directly from F2 and water, as an ecologically friendly oxidizing reagent. Tetrahedron 1993, 49 (36), 8169–78. DOI: 10.1016/S0040-4020(01)88036-4.
  7. ↑ Appelman, Evan H.; Dunkelberg, Oliver; Kol, Moshe Hypofluorous acid and acetonitrile: the taming of a reagent. J. Fluorine Chem. 1992, 56 (2), 199–213. DOI: 10.1016/S0022-1139(00)81103-3.
  8. ↑ Dennis, L. M.; Rochow, E. G. Oxyacids of Fluorine. J. Am. Chem. Soc. 1932, 54 (2), 832–33. DOI: 10.1021/ja01341a518.
  9. ↑ Dennis, L. M.; Rochow, E. G. Oxyacids of Fluorine. II. J. Am. Chem. Soc. 1933, 55 (6), 2431–34. DOI: 10.1021/ja01333a033.
  10. ↑ Noble, Paul N.; Pimentel, George C. Hypofluorous acid: Infrared spectrum and vibrational potential function. Spectrochim. Acta Part A 1968, 24 (7), 797–806. DOI: 10.1016/0584-8539(68)80177-1.

Further reading

External links

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